[理学]加州大学伯克利分校有机化学课件.ppt

? University of California ? Univesity of California Chapter 20: Carboxylic Acid Derivatives What is the relative reactivity of these carboxylic acid derivatives? Origins of Reactivity Trends Comparing Reactivity A. Alkanoyl Halides B. Anhydrides C. Esters D. Amides E. Alkanenitriles A. Alkanoyl Halides B. Anhydrides C. Esters D. Amides E. Alkanenitriles: RCN Structure Nitriles are Acidic and Basic Mass Spectrometry 2. Reduction to an amine Mechanism: 3. Reduction to an aldehyde Mechanism goes by single hydride addition to hemiaminal stage, then hydrolysis. Acidic, like carboxylic acid pKa Values higher because amide carbonyl is relatively stabilized by resonance and N is less e-negative than O. Amide Enolates and Amidates Acidic, like other carbonyl compounds Allows alkylation at N or C (if N is blocked): Only for primary amines: This constitutes a one-carbon degradation of a chain: Topologically, CO is excised. 4. Hofmann rearrangement Example: Mechanism: Recall: CHCl3 + base → -CCl3 6e species Recall: -CCl3 → CCl2 + -Cl Names: Alkanoic acid → alkanenitrile Substituent CN is called cyano Cyanocycloalkanes are called cycloalkanecarbonitriles Retained by IUPAC C and N sp-hybridized like C in alkynes 1H NMR: Spectra 13C NMR: δ ~ 112-126 ppm (close to alkene region) Higher than (δ~65-85 ppm), because N is more electronegative IR: Stretch 2250 cm-1 Compare 2120 cm-1 weaker bond pKa~ -10 RCH2CN pKa ~ 25 Alkylation of anion with RX, RC(O)H is possible: Like enolates Acidic: Basic Example: Hydrolysis: H+ or HO- to carboxylic acids Recall: General: RH ? RX ? RCN ? RCOOH Mechanisms: H+-catalyzed HO--”catalyzed” (actually need stoichiometric base, because it makes carboxylate first, before acidic work-up) Amide Use R’Li or R’MgX reagents Organometallic reagents attack nitriles to give ketones General: Ketone synthesis Example: R X C N R R O R R X General: RX ? RCN ? RCHO Use LiAlH(OR)3 or